TWI361182B - A hydroformylation process - Google Patents

Description

1361182 IX. INSTRUCTIONS OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The present invention relates to a hydroformylation process for a cyclic olefin, and more particularly to a process for recovering a ruthenium metal catalyst obtained in the process. [Prior Art]

Catalysts used in the chemical industry can be roughly classified into heterogeneous catalysts and homogeneous catalysts. Compared to heterogeneous catalysts, homogeneous catalysts have the advantages of high reactivity, high selectivity and mild reaction conditions. However, there are still many homogeneous catalyst reaction systems that cannot be commercialized. The most important factor is that homogeneous catalysts are not easily separated and recycled. In general, the minimum cost to separate different materials such as catalysts, products, starting materials and solvents should be distillation. In the distillation method, if the product is not highly volatile, it is necessary to raise the temperature to produce a separation effect. However, most homogeneous catalysts are quite sensitive to heat. They usually decompose on their own at slightly elevated temperatures and cannot be recycled. Other methods, such as chromatography or extraction, can also cause contact. Media loss. Therefore, the development of an effective, low-cost separation process is the key to promoting the competitiveness of homogeneous catalysts. The hydroformylation of an olefinic compound with carbon monoxide and hydrogen to form a complex is an important homogeneous catalytic reaction. Depending on the structural difference of the various olefinic compounds, the aldehyde compound obtained can be used not only as a chemical such as a perfume but also as an important special chemical intermediate. Through further hydrogenation, oxidation and amination reaction 1361182

Such compounds are converted into compounds such as alcohols, carboxylic acids and amines for use in specialty chemicals, plasticizers, coatings, especially ultraviolet curable resins and other optical materials. The hydroquinone reaction of olefinic compounds is usually carried out by using ruthenium or cobalt metal as a catalyst, especially a ruthenium catalyst, because the ruthenium catalyst has high reactivity and selectivity. Although the catalytic activity of the ruthenium catalyst is relatively high, since the price is much higher than that of the cobalt catalyst, how to effectively recycle and reuse the ruthenium catalyst becomes an important issue. If the product carbon number is low (<C5), the catalyst can be separated from the product by cryogenic distillation without destroying the cracking catalyst. However, if the carbon number of the product is high, it is not suitable to separate the product and the catalyst by distillation because the excessively high distillation temperature as described above easily causes cracking of the catalyst, making the expensive catalyst unreusable and increasing the production cost. The use of high-carbon aldehyde products and their derived alcohols, carboxylic acids and amines in UV-curable resins and other optical materials is on the rise, so the industry is looking for a highly efficient process to reuse catalysts to increase Product competitiveness. As described above, the product obtained by the cycloolefin in the fluorene reaction has a high boiling point, and if the product and the catalyst are separated by distillation under reduced pressure, it is carried out at a higher temperature. In this high temperature environment, the catalyst is easily decomposed due to instability, so considerable research has focused on other milder purification tasks, such as solvent extraction. In W093/02024, a high carbon number aldehyde product after the oxime catalyst and the hydroquinone reaction are separated by using a primary solvent and a water mixture as an extraction solvent. However, the separation effect is not good, and the partition coefficient of the product in the extraction solvent is low.

I 6 1361182

(Tris(2,4-di-tert-butyl phenyl) phosphite), triphenyl linphyrin (tripheny lphosphite), tris(3-mercapto-6-t-butylphenyl)phosphoric acid (tris (3) -methyl-6-tert-butylphenyl) phosphite), tris(3-methoxyl-6-tert-butylphenyl) phosphite, three (tris(3-methoxyl-6-tert-butylphenyl) phosphite) 2,4-di-tert-butylphenyl phosphate, di(2-tert-butylphenyl)-tert-butylphosphite (di (2-tert-butylphenyl)-tert-butylphosphite), or other suitable dish based source. The molar ratio of the molar catalyst to the molar compound is between 1 and 300 Å, and the molar ratio of the catalyst to the phosphorus compound is preferably 1:1 〇 to 1:15 。. Suitable solvents for the above base metals and phosphorus-based sources may be alkanes, naphthenes or other low polar solvents. In an embodiment of the invention, the solution is positively burned. Next, a cyclic olefin and an aldehyde compound are added to the above ruthenium catalyst solution to carry out an argon oximation reaction. The aldehyde compound acts as an extractant which is miscible with the cycloalkanal product and stratified with the rhodium catalyst solution after completion of the hydroquinone reaction. The carbon number of the aldehyde compound may be an alkyl or aryl aldehyde compound of 1 to 12. The weight ratio of the aldehyde compound to the cyclic olefin is from 1:2 to 1:20. In one embodiment of the invention, the weight ratio of acid compound to cyclic olefin is between 1:5 and 1:1 Torr. Next, the key metal catalyst solution is placed in a high pressure reaction dad, and a ring-shaped dilute hydrocarbon is added to carry out a hydroquinone reaction under high pressure hydrogen gas and carbon monoxide to convert the cyclic olefin into a cycloalkanal. The molar ratio of hydrogen to carbon monoxide is between 1:1 至 and 10:1, with 3:1 to 1:3 being especially preferred. The temperature of the above hydroquinone reaction is about 40C to 160. Between the 〇, which is especially good at 70 ° C to 140 ° C, 1361182

Wherein R may be an alkyl group or a substituent having a functional group such as an alcohol group, an aldehyde group or a carboxylic acid group.

After completion of the above hydroformylation reaction, the mixture is allowed to stand to separate the mixture of the ruthenium catalyst solution, the cycloalkanal product, and the aldehyde compound into two layers, one layer mainly containing a ruthenium catalyst and a solvent thereof, and the other layer mainly being a cycloalkanal. With aldehyde compounds. The above stratification has a pressure range from atmospheric pressure to lOMPa and a temperature range from 0 °C to 100 °C. The two layers of the solution are then separated to complete the so-called separation of the cycloalkanal and the ruthenium catalyst solution. The separated key catalyst solution layer can be further added with a new cyclic olefin to carry out the oximation process. The above method solves the problem of recovery and reuse of the catalyst, and effectively separates the high boiling aldehyde product from the ruthenium catalyst solution. The isolated cycloalkanal and aldehyde compound layer may be subjected to distillation to separate the cycloalkanal from the aldehyde compound. In one embodiment of the present invention, the aldehyde compound as the extract has the same chemical structure as the cycloalkanal, and the source thereof may be the product of the previous hydroformylation process. In this case, there is no need for an additional pure 10 1361182 step to separate the cycloalkanal from the aldehyde compound as an extractant. The cycloalkanal product can be further hydrogenated to form a cycloalkanol, as in Formulas 9-15.

Show.

2H2

2H2

(Form 11) (Form 12)

formula)

(Formula 14) (Formula 15) In order to make the person skilled in the art more aware of the features of the present invention, the following is exemplified in the following: 1361182 [Simplified description of the drawings] None. [Main component symbol description] No 0

Claims (1)

丄 182 No. 97135460 Amendment date: 100.7_13 Hydrogenation process, including 'Scope of the patent: L-ring olefin is added to hydrogen and carbon monoxide in the presence of a catalyst solution and a aldehyde compound, and the solution is heated to make the cycloolefin Forming a cycloalkanal; U. After completing the hydroformylation reaction, the mixture of the above solutions is divided into a first layer and a second layer, wherein the first layer substantially comprises the medium, and the 笙-E ^ And the second layer of the second layer comprises the cycloalkanal and the aldehyde compound; and the first layer and the second layer are separated. 2' The hydroformaming process as described in claim 1, wherein the solvent used is an alkane or a cycloalkane. _ i is the hydroquinone process described in the first paragraph of the patent scope of May, wherein the alkene has a mono-carbon-carbon double bond or a multiple carbon-carbon double bond, including a dicycloolefin-3, pentadiene, Dicyclohexadiene or cyclohexenal.八. As requested in the patent paradigm (4), the hydrogen methylation process, in which the pressure range of the first layer and the second layer is between 0 MPa and 5 MPa, such as the patent range f 1 The hydrogen methylation process, wherein the hydrogen and carbon oxides of the soil are between 1 MPa and 15 MPa. 0 The hydrogen methylation process described in the first paragraph of the patent scope, wherein the mouth is touched. The temperature of the media solution is between 4 〇t and aeronautical. The acid compound is described in the above-mentioned gas amount enthalpy process, and the application thereof is 15 1361182 V. No. 97135460, date of revision: 100.7.13 8. The hydrogen formazanization process as described in claim 1 of the patent application; The aldehyde compound and the cycloalkanal are separated. • 9. Hydrogenation process as described in claim 1 of the patent application. The aldehyde compound has the same chemical structure as the cycloalkanal. Amend this, more package, which